US6426375B1 - Method for ink jet recording on non-absorbing recording medium - Google Patents

Method for ink jet recording on non-absorbing recording medium Download PDF

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Publication number
US6426375B1
US6426375B1 US09/541,934 US54193400A US6426375B1 US 6426375 B1 US6426375 B1 US 6426375B1 US 54193400 A US54193400 A US 54193400A US 6426375 B1 US6426375 B1 US 6426375B1
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ink
ink jet
jet recording
ink composition
recording method
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Kazuhide Kubota
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Seiko Epson Corp
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Seiko Epson Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/21—Ink jet for multi-colour printing
    • B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
    • B41J2/2114—Ejecting specialized liquids, e.g. transparent or processing liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
    • B41M5/0017—Application of ink-fixing material, e.g. mordant, precipitating agent, on the substrate prior to printing, e.g. by ink-jet printing, coating or spraying
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0058—Digital printing on surfaces other than ordinary paper on metals and oxidised metal surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers

Definitions

  • the present invention relates to an ink jet recording method, and more particularly to an ink jet recording method wherein a reaction solution and an ink composition are deposited on a recording medium having no ink composition absorbing capacity to perform printing.
  • Ink jet recording is a printing method wherein droplets of an ink composition are ejected and deposited onto a recording medium to perform printing. This method has a feature that images having high resolution and high quality can be printed at a high speed by means of relatively inexpensive apparatuses.
  • the ink composition used in the ink jet recording comprises water as a main component and, added thereto, a colorant and a wetting agent, such as glycerin, for preventing clogging and other purposes.
  • Recording media such as papers, absorb the ink composition to permit the colorant to penetrate into and to be fixed onto the recording media.
  • the ink composition should be strongly fixed onto the surface of the recording medium.
  • the ink composition that is not strongly fixed forms images having poor rubbing/scratch resistance.
  • the time required for the formed image to be fixed onto the recording medium that is, the drying time, is preferably short. This is because the long drying time may cause a fear that the image is deteriorated upon contact of the image with members within a printer or upon contact of the image with a hand or the like after a discharge from the printer.
  • a solvent added to the ink composition should be selected so that the recording medium neither undergoes a change in quality nor is deformed by the solvent contained in the ink composition.
  • the application of a polyvalent metal salt solution onto a recording medium followed by the application of an ink composition containing a dye having at least one carboxyl group has been recently proposed (for example, Japanese Patent Laid-Open No. 202328/1993).
  • the claimed advantage of this method is that the polyvalent metal ion combines with the dye to form an insoluble complex, the presence of which can offer an image having water fastness and high quality free from color bleeding.
  • a color ink comprising at least a surfactant for imparting a penetrating property or a solvent having a penetrating property and a salt in combination with a black ink capable of being thickened or agglomerated through the action of the salt
  • Japanese Patent Laid-Open No. 106735/1994 Japanese Patent Laid-Open No. 106735/1994.
  • the claimed advantage of this method is that high-quality color images having high image density and free from color bleeding can be yielded.
  • an ink jet recording method has been proposed wherein two liquids, a first liquid containing a salt and a second liquid of an ink composition, are printed to realize good images.
  • the present inventors have now found an ink jet recording method, using two liquids, which can realize good images on recording media having no ink composition absorbing capacity.
  • the present invention has been made based on such finding.
  • an ink jet recording method comprising the steps of: depositing a reaction solution and an ink composition onto a recording medium to perform printing,
  • the recording medium does not substantially absorb the ink composition
  • the reaction solution comprises a reactant which, when brought into contact with the ink composition, produces coagulate
  • the ink composition comprises a pigment and resin emulsion having a minimum film-forming temperature of 20° C. or below, the content of the polymer particulates in the ink composition being not less than 5% by weight, the weight ratio of the polymer particulates to the pigment being 1 to 20.
  • FIG. 1 is a diagram showing an ink jet recording apparatus according to the present invention, wherein a recording head is provided separately from an ink tank to feed an ink composition and a reaction solution into a recording head through an ink tube;
  • FIG. 2 is an enlarged view of A nozzle face in a recording head, wherein reference character 1 b designates a nozzle face for a reaction solution and reference character 1 c nozzle face for ink compositions;
  • FIG. 3 is a diagram illustrating ink jet recording using the recording head shown, in FIG. 2, wherein numeral 31 designates a region where a reaction solution has been deposited and numeral 32 a printed region where an ink composition has been printed on the deposited reaction solution;
  • FIG. 4 is a diagram showing another embodiment of the recording head according to the present invention, wherein all ejection nozzles are arranged in the lateral direction;
  • FIG. 5 is a diagram showing an ink jet recording apparatus according to the present invention, wherein a recording head is integral with an ink tank;
  • FIG. 6 is a diagram showing an ink jet recording apparatus according to the present invention, wherein a heater is provided to heat a recording medium after printing.
  • the ink jet recording method according to the present invention comprises the step of printing an ink composition and a reaction solution described below onto a recording medium having substantially no ink composition absorbing capacity.
  • the recording medium according to the present invention does not substantially absorb an ink composition.
  • the “having substantially no ink composition absorbing capacity” or “does not substantially absorb an ink composition” refers to a recording medium such that an ink composition does not penetrate the recording medium at all within several sec after the deposition of the ink composition onto the recording medium.
  • recording media examples include: plastic sheets using, as a base material, polyethylene terephthalate, polycarbonate, polypropylene, polyethylene, polysulfone, ABS resin, and polyvinyl chloride; recording media prepared by coating a metal, for example, by vapor deposition, onto the surface of metals, such as brass, iron, aluminum, SUS, and copper, or non-metallic substrates; recording media prepared by subjecting paper as a substrate, for example, to water repellency-imparting treatment; recording media prepared by subjecting the surface of fibers, such as cloth, for example, to water repellency-imparting treatment; and recording media formed of the so-called “ceramic materials,” prepared by firing inorganic materials at a high temperature.
  • the contact of the reaction solution with the ink composition can realize good prints.
  • the reason why good printing can be achieved by the contact of the reaction solution with the ink composition is believed as follows.
  • the reactant contained in the reaction solution breaks the state of dispersion of a colorant, fine particles of the polymer, and other ingredients contained in the ink composition, resulting in coagulation of these ingredients.
  • the resultant coagulate is considered to strongly fix the colorant onto the surface of the recording medium.
  • the ink composition contains resin emulsion having specific properties.
  • the reaction solution and the ink composition may be applied onto the recording medium in any order.
  • suitable methods for the deposition of the reaction solution and the ink composition include a method wherein the ink composition is deposited onto the recording medium after the deposition of the reaction solution onto the recording medium, a method wherein the ink composition is first printed onto the recording medium followed by the deposition of the reaction solution onto the recording medium, and a method wherein the reaction solution and the ink composition are mixed together just before or just after the ejection.
  • the deposition of the reaction solution onto the recording medium may be carried out by any of a method wherein the reaction solution is selectively deposited onto only an area where the ink composition is deposited, and a method wherein the reaction solution is deposited on the whole area of the recording medium.
  • the former method is cost-effective because the consumption of the reaction solution can be minimized.
  • the accuracy of the position at which both the reaction solution and the ink composition are deposited should be high to some extent.
  • the method to be used may be determined by taking a combination of the ink composition with the reaction solution into consideration.
  • the reaction solution may be deposited by ink jet recording.
  • the ink composition refers to a black ink composition in the case of monochrome printing and color ink compositions in the case of color printing, specifically yellow, magenta, and cyan ink compositions, and optionally a black ink composition.
  • the ink composition used in the method according to the present invention comprises at least a pigment and resin emulsion.
  • the resin emulsion has the effect of accelerating the fixation of the pigment onto the surface of the recording medium through interaction between the resin emulsion and the reactant in the reaction solution, particularly a polyvalent metal ion, a polyallylamine, or a polyallylamine derivative. Further, some resin emulsions have the effect of forming a film on the recording medium to improve the rubbing/scratch resistance of prints.
  • the ink composition according to the present invention preferably contains a resin emulsion.
  • resin emulsion used herein refers to an emulsion comprising water as a continuous phase and the following resin component as a dispersed phase.
  • Resin components as the dispersed phase include acrylic resin, vinyl acetate resin, styrene/butadiene resin, vinyl chloride resin, acryl/styrene resin, butadiene resin, styrene resin, crosslinked acrylic resin, crosslinked styrene resin, benzoguanamine resin, phenolic resin, silicone resin, and epoxy resin.
  • resin components particle comprising of resin emulsion refer to “polymer particulates” or “resin emulsion particles”.
  • the resin emulsion has a minimum film-forming temperature of 20° C. or below.
  • the term “minimum film-forming temperature” used herein refers to a minimum temperature at which, when a resin emulsion prepared by dispersing polymer particulates in water is thinly cast onto a sheet of a metal, such as aluminum, to form a coating which is then gradually heated, a transparent, continuous film is formed.
  • a white powder is formed in a temperature region below the minimum film-forming temperature.
  • the fine particles of the polymer have a glass transition point of 10° C. or below.
  • the ink composition used in the present invention contains the polymer particulates in an amount of not less than 5% by weight, more preferably not less than 8% by weight, based on the ink composition.
  • the weight ratio of the polymer particulates to the pigment is in the range of 1 to 20, preferably in the range of 2 to 10.
  • the diameter of the polymer particulates is preferably not more than about 100 nm, more preferably about 5 to 80 nm.
  • the polymer particulates have carboxyl groups on the surface thereof and, in addition, have high reactivity with a divalent metal salt. More specifically, the polymer particulates have a reactivity with a divalent metal salt such that, when 3 volumes of a 0.1 wt % aqueous emulsion is brought into contact with one volume of a 1 mol/liter aqueous divalent metal salt solution, the time required for the transmission of light having a wavelength of 700 nm to become 50% of the initial value is not more than 1 ⁇ 10 4 sec (preferably not more than 1 ⁇ 10 3 sec, more preferably not more than 1 ⁇ 10 2 sec).
  • divalent metal ions include divalent metal ions, such as Ca 2+ , Cu 2+ , Ni 2+ , Mg 2+ , Zn 2+ , and Ba 2+ .
  • Anions, which form salts with divalent metal ions include Cl ⁇ , NO 3 ⁇ , I ⁇ , Br ⁇ , ClO 3 ⁇ , and CH 3 COO ⁇ .
  • the contact angle of an aqueous emulsion, prepared by dispersing the polymer particulates in a water medium to provide a polymer particulate concentration of 10% by weight, on a teflon sheet is not less than 70 degrees.
  • the surface tension of an aqueous emulsion, prepared by dispersing the polymer particulates in a water medium to provide a polymer particulate concentration of 35% by weight is preferably not less than 40 ⁇ 10 ⁇ 3 N/m (40 dyne/cm, 20° C.). The utilization of such resin emulsion can more effectively prevent the ink droplet trajectory directionality problem and, at the same time, can realize good prints.
  • the polymer particulates having a relatively large amount of carboxyl groups can realize better rubbing/scratch resistance and water fastness.
  • a recording medium such as paper
  • water and a water-soluble organic solvent contained in the ink composition first penetrate into the recording medium, leaving the colorant and the polymer particulates around the surface of the recording medium.
  • carboxyl groups on the surface of the polymer particulates are bonded to hydroxyl groups of cellulose constituting paper fibers.
  • the polymer particulates are strongly; adsorbed onto the paper fibers.
  • the ink composition advantageously has excellent storage stability.
  • the resin emulsion may be prepared by emulsion polymerization of a resin monomer, optionally together with a surfactant, in water.
  • a resin monomer optionally together with a surfactant
  • an emulsion of acrylic resin or styrene/acryl resin may be prepared by subjecting an ester of (meth)acrylic acid or alternatively an ester of (meth)acrylic acid in combination with styrene to emulsion polymerization in water in the presence of a surfactant.
  • the mixing ratio of the resin component to the surfactant is preferably about 1000:1 to 10:1.
  • the ink composition has better water fastness and penetrability.
  • the surfactant is not particularly limited.
  • surfactants usable herein include anionic surfactants (for example, sodium dodecylbenzenesulfonate, sodium laurylate, and ammonium salt of polyoxyethylene alkyl ether sulfates), nonionic surfactants (for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylphenyl ethers, polyoxyethylenealkylamines, and polyoxyethylenealkylamides). They may be used alone or in combination of two or more.
  • anionic surfactants for example, sodium dodecylbenzenesulfonate, sodium laurylate, and ammonium salt of polyoxyethylene alkyl ether sulfates
  • nonionic surfactants for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylphenyl ethers, polyoxyethylene
  • acetylene glycol (OLFINE Y, Surfynol 82, Surfynol 104, Surfynol 440, Surfynol 465, and Surfynol 485 (all the above products being manufactured by Air Products and Chemicals Inc.) may also be used.
  • the ratio of the resin as the component constituting the dispersed phase to water is such that the amount of water is suitably 60 to 400 parts by weight, preferably 100 to 200 parts by weight, based on 100 parts by weight of the resin.
  • the resin is a polymer having a combination of a hydrophilic segment with a hydrophobic segment.
  • the ink composition contains a thermoplastic resin in the form of a resin emulsion. Further, preferably, the thermoplastic resin, when heated at the softening or melting temperature or a higher temperature and then cooled, forms a strong film having water fastness and rubbing/scratch resistance.
  • water-insoluble thermoplastic resins include, but are not limited to, polyacrylic acid, polymethacrylic acid, an ester of polymethacrylic acid, polyethylacrylic acid, a styrene/butadiene copolymer, polybutadiene, an acrylonitrile/butadiene copolymer, a chloroprene copolymer, a fluororesin, polyvinylidene fluoride, polyolefin resin, cellulose, a styrene/acrylic acid copolymer, a styrene/methacrylic acid copolymer, polystyrene, a styrene/acrylamide copolymer, polyisobutyl acrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl acetal, polyamide, rosin resin, polyethylene, a polycarbonate, a vinylidene chloride resin, a cellulosic
  • thermoplastic resins include polyethylene wax, montan wax, alcohol wax, synthetic oxide wax, an ⁇ -olefin/maleic anhydride copolymer, animal and plant waxes such as carnauba wax, lanolin, paraffin wax, and microcrystalline wax.
  • conventional resin emulsions may also be used as the resin emulsion satisfying the above requirements.
  • resin emulsions described in Japanese Patent Publication No. 1426/1987 and Japanese Patent Laid-Open Nos. 56573/1991, 79678/1991, 160068/1991, and 18462/1992 may be used.
  • the polymer particulates contain 1 to 10% by weight of a structure derived from an unsaturated vinyl monomer having a carboxyl group and has a structure crosslinked by a crosslinkable monomer having two or more polymerizable double bonds with the content of the structure derived from the crosslinkable monomer being 0.2 to 4% by weight.
  • the polymer particulates may have a single-particle structure.
  • polymer particulates having a core/shell structure may also be utilized.
  • the core/shell structure comprises a core and a shell surrounding the core.
  • the term “core/shell structure” used herein refers to “a form such that two or more polymers having different compositions are present in a phase separated state in a particle.”
  • Forms of the core/shell structure usable in the present invention include a form wherein the core is entirely covered with the shell, a form wherein the core is partially covered with the shell, and a form wherein a part of the polymer constituting the shell forms a domain or the like within the core particle.
  • the particle may have a multi-layer. structure of three or more layers wherein at least one additional layer having a different composition is further interposed between the core and the shell.
  • the core is formed of a resin having epoxy groups
  • the shell is formed of a resin having carboxyl groups.
  • the epoxy group is reactive with the carboxyl group. These two groups are allowed to exist separately from each other. That is, the epoxy group is present in the core, while the carboxyl group is present in the shell.
  • the reduction in the amount of water and the water-soluble organic solvent causes coalescence of the polymer particulates with one another, and the polymer particulates are deformed by pressure involved in the film formation.
  • the epoxy groups in the core is bonded to the carboxyl groups in the shell to form a network structure. This can advantageously form a coating having higher strength.
  • the amount of the unsaturated vinyl monomer having an epoxy group is preferably 1 to 10% by weight. According to the present invention, a reaction of a part of the epoxy groups with a part of the carboxyl groups before the film formation is acceptable so far as the film-forming property is not lost. In the present invention, the property such that, when reactive functional groups are allowed to coexist within the polymer particulates, these groups are reacted with each other without the addition of any curing agent at the time of film formation to form a network structure, will be referred to as “self-crosslinkable.”
  • the resin emulsion used in the method according to the present invention may be prepared by conventional emulsion polymerization. Specifically, the resin emulsion may be prepared by emulsion polymerization of an unsaturated vinyl monomer in water in the presence of a polymerization catalyst and an emulsifier.
  • Unsaturated vinyl monomers usable herein include those commonly used in emulsion polymerization, such as acrylic ester monomers, methacrylic ester monomers, aromatic vinyl monomers, vinyl ester monomers, vinyl cyanide compound monomers, halogenated monomers, olefin monomers, and diene monomers.
  • acrylic esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, and glycidyl acrylate; methacrylic esters, such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n
  • an unsaturated vinyl monomer having a carboxyl group should be used.
  • Preferred examples thereof include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid. Among them, methacrylic acid is preferred.
  • Emulsifiers usable herein include anionic surfactants, nonionic surfactants, and mixtures of these surfactants.
  • crosslinkable monomers having two or more polymerizable double bonds include: diacrylate compounds, such as polyethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,6-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, polypropylene glycol diacrylate, 2,2′-bis(4-acryloxypropyloxyphenyl)propane, and 2,2′-bis(4-acryloxydiethoxyphenyl)propane; triacrylate compounds, such as trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate; te
  • acrylamides or hydroxyl-containing monomers can further improve printing stability.
  • acrylamides include acrylamide and N,N′-dimethylacrylamide.
  • hydroxyl-containing monomers include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate. They may be used alone or as a mixture of two or more.
  • the polymer particulates having a core/shell structure may be produced by conventional methods, generally multi-step emulsion polymerization and the like, for example, by a method disclosed in Japanese Patent Laid-Open No. 76004/1992.
  • unsaturated vinyl monomers usable in the polymerization include those described above.
  • Methods usable for the introduction of epoxy group into the core include a method wherein an epoxy-containing unsaturated vinyl monomer, such as glycidyl acrylate, glycidyl methacrylate, or allylglycidyl ether, is copolymerized with other unsaturated vinyl monomer, and a method wherein, in the polymerization of at least one unsaturated vinyl monomer to prepare core particles, an epoxy compound is simultaneously added to form a composite structure.
  • the former method is preferred from the viewpoints of easiness of the polymerization, polymerization stability and the like.
  • initiators In the emulsion polymerization, initiators, surfactants, molecular weight regulators, neutralizing agents and the like may be used according to a conventional method.
  • the resin emulsion may be mixed, in the form of a powder of fine particles, with other ingredients of the ink composition.
  • a preferred method is such that the polymer particulates are dispersed in a water medium to form a polymer emulsion which is then mixed with other ingredients of the ink composition.
  • the content of the polymer particulates in the ink composition is preferably about 5 to 40% by weight, more preferably about 8 to 20% by weight.
  • the ink composition contains an alginic acid derivative.
  • alginic acid derivatives include alkali metal alginates (for example, sodium salt and potassium salt), organic salts of alginic acid (for example, triethanolamine salt), and ammonium alginate.
  • the amount of the alginic acid derivative added to the ink composition is preferably about 0.01 to 1% by weight, more preferably about 0.05 to 0.5% by weight.
  • the reason why the addition of the alginic acid derivative can realize good images has not been fully elucidated yet, the reason is believed to reside in that the polyvalent metal salt present in the reaction solution reacts with the alginic acid derivative contained in the ink composition to change the state of dispersion of the colorant and consequently to accelerate the fixation of the colorant onto the recording medium.
  • the colorant contained in the ink composition used in the present invention is a pigment.
  • inorganic and organic pigments are usable.
  • examples of inorganic pigments usable herein include, in addition to titanium oxide and iron oxide, carbon blacks produced by known processes, such as contact, furnace, and thermal processes.
  • organic pigments usable herein include azo pigments (including azo lake, insoluble azo pigment, condensed azo pigment, and chelate azo pigment), polycyclic pigments (for example, phthalocyanine, perylene, perinone, anthraquinone, quinacridone, dioxazine, thioindigo, isoindolinone, and quinophthalone pigments), dye chelates (for example, basic dye chelates and acid dye chelates), nitro pigments, nitroso pigments, and aniline black.
  • azo pigments including azo lake, insoluble azo pigment, condensed azo pigment, and chelate azo pigment
  • polycyclic pigments for example, phthalocyanine, perylene, perinone, anthraquinone, quinacridone, dioxazine, thioindigo, isoindolinone, and quinophthalone pigments
  • dye chelates for example, basic dye chelates and acid dye chel
  • the above pigment is preferably added, to the ink, in the form of a pigment dispersion prepared by dispersing the pigment in an aqueous medium with the aid of a dispersant or a surfactant.
  • Preferred dispersants usable herein include those commonly used in the preparation of a dispersion of a pigment, for example, polymeric dispersant.
  • the dispersant and the surfactant contained in the dispersion of the pigment function also as the dispersant and the surfactant for the ink composition.
  • the amount of the pigment added to the ink is preferably about 0.5 to 25% by weight, more preferably about 2 to 15% by weight.
  • the ink composition further contains an organic solvent.
  • the organic solvent is preferably a low-boiling organic solvent. Preferred examples thereof include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, sec-butanol, tert-butanol, iso-butanol, and n-pentanol. Monohydric alcohols are particularly preferred.
  • the low-boiling organic solvent has the effect of shortening the drying time of the ink.
  • the ink composition used in the present invention further contains a wetting agent comprising a high-boiling organic solvent.
  • high-boiling organic solvents include: polyhydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerin, trimethylolethane, and trimethylolpropane; alkyl ethers of polyhydric alcohols, such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol monobutyl ether; urea
  • the amount of the wetting agent added is preferably 0.5 to 40% by weight, more preferably 2 to 20% by weight, based on the ink.
  • the amount of the low-boiling organic solvent added is preferably 0.5 to 10% by weight, more preferably 1.5 to 6% by weight, based on the ink.
  • the ink composition used in the present invention may contain a dispersant and a surfactant.
  • surfactants usable herein include various surfactants described above in connection with the resin emulsion.
  • the ink composition contains a saccharide.
  • saccharides usable herein include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), and other polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol, sorbitol, maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose.
  • polysaccharide used herein means saccharides in the broad sense as including substances which exist widely in the world of nature, such as alginic acid, ⁇ -cyclodextrin, and cellulose.
  • saccharides usable herein include reducing sugars of the above saccharides (for example, sugar alcohols represented by the general formula HOCH 2 (CHOH) n CH 2 OH, wherein n is an integer of 2 to 5), oxidizing sugars (for example, aldonic acid or uronic acid), amino acids, and thiosugars.
  • sugar alcohols are particularly preferred, and specific examples thereof include maltitol and sorbitol.
  • the content of the saccharide is suitably 0.1 to 40% by weight, preferably 0.5 to 30% by weight, based on the ink composition.
  • pH adjustors may be added to the ink composition used in the present invention.
  • the reaction solution used in the present invention contains a reactant that can break the state of dispersion and/or dissolution of the pigment, the resin emulsion and the like in the ink composition to cause coagulation of the pigment, the resin emulsion and the like.
  • reactants usable herein include polyvalent metal salts, polyamines, and polyamine derivatives.
  • the polyvalent metal salt usable in the reaction solution is a salt that is constituted by divalent or higher polyvalent metal ions and anions bonded to the polyvalent metal ions and is soluble in water.
  • polyvalent metal ions include divalent metal ions, such as Ca 2+ , Cu 2+ , Ni 2+ , Mg 2+ , Zn 2+ , and Ba 2+ , trivalent metal ions, such as Al 3 +, Fe 3 +, and Cr 3 +.
  • Anions include Cl ⁇ , No 3 ⁇ , I ⁇ , Br ⁇ , ClO 3 ⁇ , and CH 3 COO ⁇ .
  • a metal salt constituted by Ca 2+ or Mg 2+ provides favorable results in terms of pH of the reaction solution and the quality of prints.
  • the concentration of the polyvalent metal salt in the reaction solution may be suitably determined so as to attain the effect of providing good print quality and preventing clogging. It, however, is preferably about 0.1 to 40% by weight, more preferably about 5 to 25% by weight.
  • the polyvalent metal salt contained in the reaction solution is constituted by divalent or higher polyvalent metal ions and nitrate ions or carboxylate ions bonded to the polyvalent metal ions and is soluble in water.
  • the carboxylate ions are derived from a saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms or a carbocyclic monocarboxylic acid having 7 to 11 carbon atoms.
  • Preferred examples of the saturated aliphatic monocarboxylic acid having 1 to 6 carbon atoms include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, and hexanoic acid. Among them, formic acid and acetic acid are particularly preferred.
  • a hydrogen atom(s) on the saturated aliphatic hydrocarbon group in the monocarboxylic acid may be substituted by a hydroxyl group.
  • Preferred examples of such carboxylic acids include lactic acid.
  • carbocyclic monocarboxylic acid having 6 to 10 carbon atoms include benzoic acid and naphthoic acid with benzoic acid being more preferred.
  • Polyallylamine and polyallylamine derivative usable in the reaction solution are cationic polymers which are soluble in water and can be positively charged in water.
  • Such polymers include, for example, those represented by the following formulae (I), (II), and (III):
  • X ⁇ represents chloride, bromide, iodide, nitrate, phosphate, sulfate, acetate or other ions.
  • a copolymer of an allylamine with a diallylamine and a copolymer of diallylmethylammonium chloride with sulfur dioxide may also be used.
  • the content of the polyallylamine and the polyallylamine derivative is preferably 0.5 to 10% by weight based on the reaction solution.
  • the reaction solution may further contain a polyol in addition to the polyvalent metal salt.
  • the polyol has a vapor pressure of not more than 0.01 mmHg at 20° C., and the amount of the polyol added is such that weight ratio of the polyol to the polyvalent metal salt is not less than 1, preferably 1.0 to 5.0. Further, according to a preferred embodiment of the present invention, the amount of the polyol added is not less than 10% by weight, more preferably about 10 to 30% by weight, based on the reaction solution.
  • preferred polyols usable herein include polyhydric alcohols, for example, glycerin, diethylene glycol, triethylene glycol, 1,5-pentanediol, and 1,4-butanediol.
  • Further specific examples of preferred polyols include saccharides, for example, monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), and other polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol, sorbitol, maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose.
  • polyols may be added alone or as a mixture of two or more.
  • the amount of these polyols added is such that the weight ratio of the total amount of the polyols to the polyvalent metal salt is not less than 1.
  • the reaction solution comprises a wetting agent comprising a high-boiling organic solvent.
  • the high-boiling organic solvent functions to prevent the reaction solution from drying out, thereby preventing clogging of the head.
  • Preferred examples of high-boiling organic solvents usable herein, some of which are described above in connection with the polyol include: polyhydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerin, trimethylolethane, and trimethylolpropane; alkyl ethers of polyhydric alcohols, such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono
  • the amount of the. high-boiling organic solvent added is not particularly limited, it is preferably about 0.5 to 40% by weight, more preferably about 2 to 20% by weight.
  • the reaction solution may further contain a low-boiling organic solvent.
  • a low-boiling organic solvent examples include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, sec-butanol, tert-butanol, iso-butanol, and n-pentanol. Monohydric alcohols are particularly preferred.
  • the low-boiling organic solvent has the effect of shortening the time required for drying the ink composition.
  • the amount of the low-boiling organic solvent added is preferably 0.5 to 10% by weight, more preferably 1.5 to 6% by weight.
  • the reaction solution may further contain a penetrant.
  • Penetrants usable herein include various surfactants, such as anionic, cationic, and amphoteric surfactants; alcohols, such as methanol, ethanol, and iso-propyl alcohol; and lower alkyl ethers of polyhydric alcohols, such as ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether, and dipropylene glycol monobutyl ether.
  • More preferred penetrants usable in the present invention are compounds represented by formula (IV) and/or lower alcohol ethers of polyhydric alcohols.
  • R 1 , R 2 , R 3 , and R 4 each independently represent an alkyl group.
  • Typical compounds represented by formula (IV) include OLFINE Y, Surfynol 82, Surfynol 440, Surfynol 465, and Surfynol 485 (all the above products being manufactured by Air Products and Chemicals Inc.). They may be added alone or in combination of two or more.
  • the reaction solution contains triethanolamine for pH adjustment purposes.
  • the amount of the triethanolamine added is preferably about 0 to 2.0% by weight.
  • the colorant described above in connection with the ink composition may be added to the reaction solution so that the colored reaction solution functions also as an ink composition.
  • FIG. 1 is a diagram showing an embodiment of an ink jet recording apparatus.
  • an ink composition and a reaction solution are accommodated in a tank and fed into a recording head through an ink tube.
  • a recording head 1 is communicated with an ink tank 2 through an ink tube 3 .
  • the interior of the ink tank 2 is partitioned, and a chamber for an ink composition, optionally a plurality of chambers respectively for a plurality of color ink compositions, and a chamber for a reaction solution are provided.
  • the recording head 1 is moved along a carriage 4 by means of a timing belt 6 driven by a motor 5 .
  • a recording medium 7 is placed by a platen 8 and a guide 9 at a position facing the recording head 1 .
  • a cap 10 is provided.
  • a suction pump 11 is connected to the cap 10 in order to conduct the so-called “cleaning operation.”
  • the ink composition sucked by the suction pump 11 is resorquestionedd in a waste ink tank 13 through a tube 12 .
  • FIG. 2 is an enlarged view showing the surface of nozzles for the recording head 1 .
  • the surface of a nozzle for a reaction solution is indicated by 1 b, and a nozzle 21 for ejecting the reaction solution is provided in the longitudinal direction.
  • the surface of nozzles for the ink composition is indicated by 1 c, and a yellow ink composition, a magenta ink composition, a cyan ink composition, and a black ink composition are ejected respectively through nozzles 22 , 23 , 24 and 25 .
  • the recording head 1 is moved in the direction indicated by an arrow A, during which time the reaction solution is ejected through the nozzle surface 1 b to form a reaction solution-deposited region 31 in a band form on the recording medium 7 . Subsequently, the recording medium 7 is transferred by a predetermined extent in the recording medium feed direction indicated by an arrow B, during which time the recording head 1 is moved in the direction opposite to that indicated by the arrow A in the drawing and returned to the left end of the recording medium 7 , and the recording head 1 conducts printing using the ink composition on the reaction solution-deposited region, thereby forming a print region 32 .
  • the recording head 1 it is also possible to arrange all nozzles in the lateral direction to construct a nozzle assembly.
  • ejection nozzles for a reaction solution are denoted by 41 a and 41 b, and a yellow ink composition, a magenta ink composition, a cyan ink composition, and a black ink composition are ejected respectively through nozzles 42 , 43 , 44 and 45 .
  • the recording head 1 when reciprocated on the carriage, can conduct printing in both directions. Therefore, in this case, printing at a higher speed is expected as compared with the case where the recording head shown in FIG. 2 is used.
  • Regulating the surface tension of the reaction solution and the ink composition preferably by the above method enables a high-quality print to be more stably provided independently of the order of depositing the reaction solution and the ink composition.
  • use of only one ejection nozzle for the reaction solution suffices for desired results (for example, the nozzle indicated by numeral 41 b in the drawing may be omitted), leading to a further reduction in size of head and an increase in printing speed.
  • the supplement of the ink composition may be carried out by replacing a cartridge as an ink tank.
  • the ink tank may be integral with the recording head.
  • FIG. 5 A preferred embodiment of an ink jet recording apparatus using such an ink tank is shown in FIG. 5 .
  • recording heads 1 a and 1 b are integral respectively with ink tanks 2 a and 2 b.
  • An ink composition and a reaction solution are ejected respectively through the recording heads 1 a and 1 b.
  • printing may be conducted in the same manner as described above in connection with the apparatus shown in FIG. 1 .
  • the recording head 1 a is moved together with the ink tank 2 a on a carriage 4
  • the recording head 1 b is moved together with the ink tank 2 b on the carriage 4 .
  • FIG. 6 A preferred embodiment of an ink jet recording apparatus wherein a heater for heating a printed recording medium is provided is shown in FIG. 6 .
  • the embodiment shown in FIG. 6 is the same as the embodiment shown in FIG. 1, except that a heater 14 is additionally provided.
  • the heater 14 may be of a contact type wherein, in heating the recording medium, it is brought into contact with the recording medium.
  • the heater 14 may be of a non-contact type where the recording medium is heated by applying infrared rays or the like or blowing hot air to the recording medium.
  • the ink was prepared as follows. The carbon black, the dispersant, and a part of water were mixed together, and the mixture, together with glass beads (diameter: 1.7 mm, amount: 1.5 times (by weight) larger than the mixture), was dispersed for 2 hr in a sand mill (manufactured by Yasukawa Seisakusho). Thereafter, the glass beads were removed to prepare a dispersion of carbon black. Separately, all the above ingredients except for the carbon black, the dispersant and the part of water used in the preparation of the carbon black dispersion were mixed together to pre pare an ink solvent. The ink solvent was gradually added dropwise to the carbon black dispersion while stirring the dispersion. The mixture was stirred at room temperature for 20 min. The mixture was filtered through a 5- ⁇ m membrane filter to prepare an ink for ink jet recording.
  • Pigment Blue 15:3 2 wt % Styrene/acrylic acid copolymer (dispersant) 1 wt % Voncoat 4001 (acrylic resin emulsion, 10 wt % resin component 50%, MFT 5° C., manufactured by Dainippon Ink and Chemicals, Inc.) Diethylene glycol 10 wt % Ion-exchanged water Balance Magenta ink A1 C.I.
  • Pigment Red 122 3 wt % Styrene/acrylic acid copolymer (dispersant) 1 wt % Voncoat 5454 (styrene/acrylic resin emulsion, 20 wt % resin component 45%, MFT 4° C., manufactured by Dainippon Ink and Chemicals, Inc.) Glycerin 8 wt % Ion-exchanged water Balance Yellow ink A1 C.I.
  • Pigment Yellow 74 3.5 wt % Styrene/acrylic acid copolymer (dispersant) 1 wt % Voncoat 4001 (acrylic resin emulsion, 15 wt % resin component 50%, MFT 5° C., manufactured by Dainippon Ink and Chemicals, Inc.)
  • Glycerin 8 wt % Ion-exchanged water Balance Color ink set A2 Cyan ink A2 Pigment: KET BLUE EX-1 (manufactured by 3 wt % Dainippon Ink and Chemicals, Inc.) Styrene/acrylic acid copolymer (dispersant) 1 wt % Microgel E-5002 (styrene/acrylic resin 7 wt % emulsion, resin component 29.2%, MFT 80° C., manufactured by Nippon Paint Co., Ltd.)
  • Reaction solution A2 Polyallylamine PAA-HCL-3L (resin component 50%, 20 wt % manufactured by Nitto Boseki Co., Ltd.) Diethylene glycol 15 wt % Ion-exchanged water Balance The above ingredients were mixed together to prepare a reaction solution A2.
  • Printing was carried out using the inks 1 to 3, the color ink sets 1 and 2, and the reaction solution 1 by means of an ink jet printer MJ-930C (manufactured by Seiko Epson Corp.) on a PET film.
  • MJ-930C manufactured by Seiko Epson Corp.
  • the reaction solution, the black ink, and the color ink were simultaneously printed at 100% duty on a PET film, and the prints were visually inspected for uneven color mixing in boundaries of different colors.
  • the results were evaluated according to the following criteria.
  • the reaction solution, the black ink, and the color ink were simultaneously printed at 100% duty on a PET film.
  • the records thus obtained were allowed to stand at room temperature for one day. Thereafter, the printed face was strongly rubbed with a finger.
  • the results were evaluated according to the following criteria.
  • Evaluation A3 Fixation of ink by heating The reaction solution, the black ink, and the color ink were simultaneously printed at 100% duty on a PET film. Immediately after the printing, the recording medium was heated from the backside by means of a heater at 50° C. for 5 sec. Immediately after the heating, the printed face of the recording medium was strongly rubbed with a finger. The results were evaluated according to the following criteria.
  • a reactor equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 370 g of pure water and 1 g of sodium dodecylbenzenesulfonate. 2.3 g of potassium persulfate was added to the system at a temperature of 70° C. in a nitrogen atmosphere with stirring.
  • three-phase emulsion monomers having the following compositions were separately provided.
  • a mixture of 36.0 g of pure water, 0.2 g of sodium dodecylbenzenesulfonate, 38.6 g of styrene, 32.9 g of butyl acrylate, 22.5 g of glycidyl methacrylate, and 0.1 g of t-dodecylmercaptan was provided as the first phase.
  • a mixture of 72.0 g of pure water, 0.4 g of sodium dodecylbenzenesulfonate, 93.2 g of styrene, 88.8 g of butyl acrylate, and 0.2 g of t-dodecylmercaptan was provided as the second phase.
  • a mixture of 72.0 g of pure water, 0.4 g of sodium dodecylbenzenesulfonate, 57.6 g of styrene, 110.9 g of butyl acrylate, 30 g of methacrylic acid, and 0.2 g of t-dodecylmercapatan was provided as the third phase.
  • the first emulsion monomer was added dropwise to the above aqueous solution, followed by digestion. Further, for the second phase and the third phase, the dropwise addition of the emulsion monomer and the digestion were repeated.
  • the dropping time was 3 hr for the first phase, 2 hr for the second and third phases, and, for each phase, the digestion time was 2 hr.
  • the aqueous resin emulsion thus obtained was cooled to room temperature, and ion-exchanged water and aqueous ammonia were then added thereto to adjust the aqueous resin emulsion to solid content 35% by weight and pH 8.
  • the aqueous resin emulsion thus obtained had a minimum film-forming temperature of about 18° C., a surface tension of 57 ⁇ 10 ⁇ 3 N/m, a contact angle of 89 degrees, a particle diameter of 0.09 ⁇ m, and a half value period in a reaction with Mg 2+ ions of 10 sec.
  • Ink compositions were prepared according to the following formulations. Specifically, the ink was prepared as follows.
  • the pigment, the dispersant, and a part of water were mixed together, and the mixture, together with glass beads (diameter: 1.7 mm, amount: 1.5 times (by weight) larger than the mixture), was dispersed for 2 hr in a sand mill (manufactured by Yasukawa Seisakusho). Thereafter, the glass beads were removed to prepare a pigment dispersion.
  • all the above ingredients except for the carbon black, the dispersant and the part of water used in the preparation of the pigment dispersion were mixed together to prepare an ink solvent.
  • the ink solvent was gradually added dropwise to the pigment dispersion while stirring the pigment dispersion.
  • the mixture was stirred at room temperature for 20 min.
  • the mixture was filtered through a 5- ⁇ m membrane filter to prepare an ink composition for ink jet recording.
  • Ink composition B1 Carbon Black MA 7 (manufactured by 5 wt % Mitsubishi Chemical Corporation) Styrene/acrylic acid copolymer (dispersant) 1 wt % Aqueous resin emulsion B prepared above 10 wt % (in terms of concentration of fine particles of polymer) Glycerin 10 wt % Ion-exchanged water Balance Ink composition B2 C.I. Pigment Black 1 1 wt % Styrene/acrylic acid copolymer (dispersant) 1 wt % Glycerin 15 wt % Ion-exchanged water Balance Color ink set B1 Cyan ink B1 C.I.
  • the reaction solutions B, the ink compositions B, and the color ink sets B were used in combination as indicated in Table 3 to perform printing on a PET film by means of an ink jet printer MJ-930C manufactured by Seiko Epson Corp.
  • the reaction solution, the black ink, and the color ink were simultaneously printed at 100% duty on a PET film, and the prints were visually inspected for uneven color mixing in boundaries of different colors.
  • the results were evaluated according to the following criteria.
  • the reaction solution, the black ink, and the color ink were simultaneously printed at 100% duty on a PET film.
  • the records thus obtained were allowed to stand at room temperature for one day. Thereafter, the printed face was strongly rubbed with a finger to evaluate the fixation of ink.
  • the reaction solution, the black ink, and the color ink were simultaneously printed at 100% duty on a PET film.
  • the recording medium was heated from the backside by means of a heater at 50° C. for 5 sec.
  • the printed face of the recording medium was strongly rubbed with a finger to evaluate the fixation of ink.

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EP1041126A3 (de) 2002-01-30
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